CN105233852B - A kind of GaN/CQDS composite photo-catalysts and its preparation method and application - Google Patents
A kind of GaN/CQDS composite photo-catalysts and its preparation method and application Download PDFInfo
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Abstract
A kind of GaN/CQDS composite photo-catalysts of the present invention, are made up of GaN and carbon quantum dot CQDS, and in the catalyst, GaN mass percent is 99.99% 90%, and carbon quantum dot CQDS mass percent is 0.01% 10%.Present invention also offers a kind of preparation method of above-mentioned GaN/CQDS composite photo-catalysts, first using GaN and Ga2O3It is mixed with mixing gallium source；Then mixing gallium source is added in a reaction vessel and carries out chemical vapor deposition preparation GaN nano wire；CQDS is prepared again；CQDS and GaN nano wire are mixed according to mass percent, stirred, be positioned over after stirring in ultrasonic instrument it is ultrasonic, then by mixture it is dry GaN CQDS composite photo-catalysts.The photochemical catalyst of the present invention has higher catalytic efficiency and faster Catalysis Rate than the single GaN photochemical catalysts of same type to analyte.
Description
Technical field
The invention belongs to chemical field, is related to a kind of catalyst, specifically a kind of GaN/CQDS composite photo-catalysts
And its preparation method and application.
Background technology
With the aggravation of the especially water pollution problems of the environmental pollution in global range, environmental photocatlytsis solves as scientist
A certainly important research direction of pollution problem.Report and be unequal to piece both at home and abroad with the correlative study of photocatalytic degradation organic matter at present
Lift, because light-wave energy can be changed into chemical energy by the reaction system of photocatalysis technology under illumination condition, therefore many is just
The reaction being difficult under the conditions of often, can also smoothly occur and continue to carry out at ambient temperature.And in semiconductor light
In the presence of catalyst, Some Organic Pollutants directly can be decomposed into inorganic matter, H by sunshine2O and CO2, Er Qieguang
Catalyst does not pollute in itself, and photocatalysis technology has reached the purpose for the substance decomposition for making environment harmful, without bringing
Others pollution.Nano material has a suitable energy gap, high draw ratio, the advantages that high specific surface area, is advantageous to light
The raising of catalytic activity, it is widely used in photocatalysis field, but some drawbacks again be present in itself, such as zinc oxide is as light
Catalyst is commonly used, but has that fast light corrosivity is poor, and the shortcomings of harsh is required to environment pH values.Conventional means is mainly led to
Overdoping and surface modification are to adjust band structure, improve its performance to solve the above problems.Recent studies have shown that GaN
Base monodimension nanometer material is due to high specific surface area, being widely used to laser, light emitting diode, field effect transistor
Pipe, photo-detector etc..At present, the photoelectric properties of GaN material have received extensive research, but the report of its photocatalysis performance
Then seldom, its stable physicochemical properties to photochemical catalyst in itself for important in inhibiting.And the carbon quantum of smaller yardstick
Point is because of the peculiar property of its outstanding bio-compatibility, good Photoinduced Electron transmission capacity etc., opposing metallic quantum
For point, carbon quantum dot nonhazardous effect, the harm very little to environment, preparation cost is cheap, therefore, stable between GaN material
Physicochemical properties and the features such as CQDs cheap and good bio-compatibilities, will have very by preparing composite photo-catalyst
High novelty and attraction.
Chemical vapour deposition technique is to prepare one of the most frequently used method of nano structural material, this side for preparation method
Method has the characteristics that crystallinity and taking property are good and easy to operate compared with other method.Meanwhile carbon quantum dot preparation process is non-
It is often simple, inexpensively, more conducively realize and quantify.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of GaN/CQDS composite photo-catalysts and its
Preparation method and application, described this GaN/CQDS composite photo-catalysts and its preparation method and application solve prior art
In the fast light corrosivity of photochemical catalyst it is poor, harsh technical problem is required to environment pH values.
The invention provides a kind of GaN/CQDS composite photo-catalysts, it is made up of GaN and carbon quantum dot CQDS, described
In catalyst, GaN mass percent is 99.99%-90%, and described carbon quantum dot CQDS mass percent is 0.01%-
10%；Described GaN is nano thread structure, a diameter of 60-120nm of the nano wire.
Preferably, in described catalyst, GaN mass percent is 99.9%, the quality hundred of described carbon quantum dot
Divide than being 0.1%；
Present invention also offers a kind of preparation method of above-mentioned GaN/CQDS composite photo-catalysts, comprise the following steps：
1) GaN of purity more than the 99.999% and Ga of purity more than 99.999% is weighed2O3 , GaN and Ga2O3Mass ratio
For 1.5-2.5:1, ground after mixing, it is 700-900nm that particle diameter, which is made, and length is 1.5-2.5um mixing gallium source；
2) step 1 is weighed）The mixing gallium source of acquisition, add in a reaction vessel, with silicon chip or Al2O3 For substrate, enter
Row chemical vapor deposition prepares GaN nano wire, and the control parameter of above-mentioned chemical vapour deposition technique process is：Growth temperature 1000-
1100 DEG C, growth time 25-35min, 25-35 DEG C of programming rate/min, argon flow amount 10-20sccm, ammonia flow 10-
30sccm；
3) the step of preparation carbon quantum dot CQDS, weighs charcoal and is positioned in another reaction vessel, adds nitre
Acid solution, is positioned in ultrasonic instrument ultrasonic, takes supernatant to add aqueous slkali and adjusts pH value to neutrality, then by supernatant from
The heart, brown supernatant is obtained, brown supernatant is dried, obtain carbon quantum dot CQDS；
4) CQDS and GaN nano wire are mixed according to mass percent, stirred, is positioned over after stirring in ultrasonic instrument,
Control frequency to carry out ultrasonic 20-40min for 150-250W, then mixture is positioned in vacuum drying chamber and controls temperature 80-
105 DEG C of dry 10-30h, obtain GaN-CQDS composite photo-catalysts.
Further, described aqueous slkali is NaOH solution, and its mass percent concentration is 10-30%.
Further, the concentration of described salpeter solution is 4-6mol/L.
Further, step 3）In, the quality mol ratio of described charcoal and nitric acid is 2g:2~3mol.
Present invention also offers a kind of above-mentioned GaN/CQDS composite photo-catalysts in photocatalytic degradation organic matter rhodamine B
In purposes.
Specifically, in use, it is 1 according to GaN/CQDS composite photo-catalysts and the mass ratio of rhodamine B:100 ratio
Calculate.
The present invention is by GaN and carbon quantum dot successively blended, stirring, ultrasound, dried, and produces photochemical catalyst, the light is urged
Agent than the single GaN photochemical catalysts of same type have to analyte higher catalytic efficiency (contrast single GaN photochemical catalysts its
Efficiency improves 1.22 times) and faster Catalysis Rate（Contrast single its Catalysis Rate of GaN photochemical catalysts and accelerate 0.8 times）.
There is higher catalytic efficiency and faster Catalysis Rate to rhodamine B.
The present invention compares with prior art, and its technological progress is significant.The photochemical catalyst of the present invention, due to huge
Specific surface area, it is adding less and catalytic effect is high, there is huge environment protection significance and value.The system of the photochemical catalyst of the present invention
Standby technique is simple, raw material is easy to get.
Brief description of the drawings
Fig. 1 is the absorption curve of GaN-CQDS composite photocatalyst for degrading rhodamine B solution.
Fig. 2 is the degradation curve of the rhodamine B degradation solution of GaN-CQDS composite photo-catalysts.
Fig. 3 be the rhodamine B degradation solution of GaN-CQDS composite photo-catalysts kinetics calculated curve and
The bar graph of the rhodamine B degradation solution of GaN-CQDS composite photo-catalysts.
Embodiment
The present invention is expanded on further below by case study on implementation and with reference to accompanying drawing, but is not intended to limit the present invention.
Embodiment 1
A kind of preparation method of GaN/CQDS composite photo-catalysts, comprises the following steps：
1) with the GaN of the purity 99.999% and Ga of purity 99.999%2O3Ga in mass ratio2O3：GaN is 2:Ground after 1 mixing
Mill, it is 700-900nm that particle diameter, which is made, and length is 1.5-2.5um mixing gallium source.
2) step 1 is weighed）Middle material 0.12g, is poured into porcelain boat, to plate the silicon chip of noble metal or Al2O3 For substrate, enter
Row chemical vapor deposition prepares GaN nano wire；The control parameter of above-mentioned chemical vapour deposition technique process is as follows：Growth temperature is
1000-1100 DEG C, growth time 30min, programming rate 30 DEG C/min, argon flow amount 10-20sccm, ammonia flow 10-
30sccm。
3) CQDS preparation：Take a certain amount of charcoal to be positioned in beaker, add a certain amount of salpeter solution, described wood
Carbonaceous amount is 0.2g, 5mol/L salpeter solution 50ml, is positioned over ultrasound in ultrasonic instrument, takes supernatant to add NaOH alkali solubles
Liquid adjusts pH value to neutrality, and solution after reaction is placed in centrifuge and centrifuged, brown supernatant is obtained, brown supernatant is placed
Dried in vacuum drying chamber, obtain CQDS.
4) by GaN nano wire in step 1) and CQDS according to three kinds of ratios 99.99%：0.01%、99.9% ：0.1%、99%
：30min is stirred after 1% mixing, controls frequency to carry out ultrasonic 30min for 200W, the dry 24h of 100 DEG C of temperature is then controlled, obtains light
Catalyst, i.e. GaN-CQDS composite photo-catalysts.
The photocatalysis of embodiment 2 is tested
The GaN-CQDS composite photo-catalysts of gained are respectively used to the photocatalysis drop of organic matter rhodamine B in Example 1
Solution, is comprised the following steps that：
1) GaN-CQDS composite photo-catalysts, the pure GaN nano wires of 10mg of the gained of 10mg above-described embodiments 1 are taken respectively
Solid powder is placed in four light-catalyzed reaction test tubes, is separately added into 50ml concentration as in the 10mg/L rhodamine B aqueous solution；
2) above-mentioned four light-catalyzed reaction test tubes are positioned in photo catalysis reactor, open magnetic stirring apparatus, first for
Dark reaction 30min in the case of uviol lamp is opened, the mixed solution that 5mL is taken out with liquid-transfering gun is placed in centrifuge tube, terminates in dark reaction
After open uviol lamp（Power 200W uviol lamps）, continuous light is carried out to the rhodamine B aqueous solution added with photochemical catalyst.Hold every time
Light source is closed after continuous illumination 10min, the mixed solution that 5mL is taken out with liquid-transfering gun is placed in centrifuge tube, continues 50min until reacting
Stop experiment afterwards.
3) centrifuge tube is centrifuged, centrifugal speed 1200r/min, centrifuges 5min；
4) supernatant that centrifugation finishes is placed in ultraviolet visible light spectrometer（UV-2550）In, due to the feature of rhodamine B
Absworption peak observes the change of its light absorption value here at 554nm.
Absorption curve such as Fig. 1 institutes after the GaN-CQDS composite photocatalyst for degrading rhodamine Bs of the gained of above-described embodiment 1
Show, find out that pure GaN nano wire reaches to its poor degradation rate after 40min of degradation effect of rhodamine B from Fig. 1-a
81.03%, and just reach 96.5% after 50min.And the photocatalysis performance of GaN/CQDS complexs all improves, wherein
As proportioning is 99.9% in Fig. 1-c：The degradation rate highest of 0.1% GaN/CQDS complexs, it is after 30min under ultraviolet lighting
The degradation rate of rhodamine B has reached the degradation rate after 94.26%, 40min and has reached 98.8%, as 99.99% in Fig. 1-b：0.01%
The degradation rates of GaN/CQDS complexs reached 94% after 30min, as 99% in Fig. 1-d：1% GaN/CQDS complexs
Degradation rate has reached 87.56% after 30min.As can be seen from Figure 1 composite catalyst has good catalytic effect.
The GaN-CQDS composite photo-catalysts and pure GaN nano wire solid powder rhodamine B degradation of the gained of above-described embodiment 1
Degradation curve afterwards is as shown in Fig. 2 fixing to GaN rhodamine B degradations generation one after as can be seen from Figure 2 adding CQDS
Ring, the degradation rate with the increase rhodamine B of CQDS amounts is accelerated by gradual, but anti-after CQDS amount reaches certain value
And its reduction of speed rate is restricted, be indicated above the appropriate CQDS of addition has significant enhancing effect to GaN photocatalysis efficiency.
GaN-CQDS composite photo-catalysts, the pure GaN nano wire solid powder rhodamine B degradation of the gained of above-described embodiment 1
Kinetics calculated curve and bar graph afterwards is urged GaN light as shown in figure 3, further demonstrating appropriate CQDS respectively
Change the raising of efficiency.
In summary, the GaN-CQDS composite photo-catalysts of gained are relative to pure GaN nano wire solid powder photochemical catalyst
With outstanding absorbing ability, it possesses the ability of more preferable photocatalytic degradation organic matter, meanwhile, with increase sieve of CQDS amounts
Red bright B degradation rate is accelerated by gradual, but restricts its reduction of speed rate on the contrary after CQDS amount reaches certain value, and both
The ratio of being best suitable for GaN/CQDS is 99.9%：When 0.1%, single GaN or CQDS photochemical catalyst pair of the photocatalysis effect than same type
Analyte has higher catalytic efficiency (contrast single its efficiency of GaN photochemical catalysts and improve 1.22 times) and faster catalysis speed
Degree（Contrast single its Catalysis Rate of GaN photochemical catalysts and accelerate 0.8 times）.
The above is only the basic explanation under present inventive concept, and is made according to technical scheme any etc.
Effect conversion, all should belong to protection scope of the present invention.
Claims (5)
1. a kind of preparation method of GaN/CQDS composite photo-catalysts, it is characterised in that comprise the following steps：
1）Weigh the GaN of purity more than the 99.999% and Ga of purity more than 99.999%2O3 , GaN and Ga2O3Mass ratio be
0.5:1, ground after mixing, it is 700-900nm that particle diameter, which is made, and length is 1.5-2.5um mixing gallium source；
2）Weigh step 1）The mixing gallium source of acquisition, add in a reaction vessel, with silicon chip or Al2O3 For substrate, changed
Learn vapour deposition and prepare GaN nano wire, the control parameter of above-mentioned chemical vapour deposition technique process is：Growth temperature 1000-1100
DEG C, growth time 25-35min, 25-35 DEG C of programming rate/min, argon flow amount 10-20sccm, ammonia flow 10-30sccm；
3) the step of preparation carbon quantum dot CQDS, weighs charcoal and is positioned in another reaction vessel, and it is molten to add nitric acid
Liquid, is positioned in ultrasonic instrument ultrasonic, takes supernatant to add aqueous slkali and adjusts pH values to neutrality, then centrifuges supernatant,
Brown supernatant is obtained, brown supernatant is dried, obtains carbon quantum dot CQDS；
4) carbon quantum dot CQDS and GaN nano wire are mixed according to mass percent, stirred, ultrasonic instrument is positioned over after stirring
In, control frequency to carry out ultrasonic 20-40min for 150-250W, then mixture is positioned in vacuum drying chamber and controls temperature
80-105 DEG C of dry 10-30h, obtains GaN-CQDS composite photo-catalysts；In described catalyst, GaN mass percent is
99.9%, described carbon quantum dot CQDS mass percent are 0.1%；Described GaN is nano thread structure, the nano wire
A diameter of 60-120nm.
A kind of 2. preparation method of GaN/CQDS composite photo-catalysts according to claim 1, it is characterised in that：Described
Aqueous slkali is NaOH solution, and its mass percent concentration is 10-30%.
A kind of 3. preparation method of GaN/CQDS composite photo-catalysts according to claim 1, it is characterised in that：Described
The concentration of salpeter solution is 4-6mol/L.
4. a kind of GaN/CQDS composite photo-catalysts that the method according to claim 11 prepares have in photocatalytic degradation
Purposes in machine thing rhodamine B.
5. purposes according to claim 4, it is characterised in that：In use, according to GaN/CQDS composite photo-catalysts and sieve
Red bright B mass ratio is 1:100 ratio calculates.
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